钴铁双金属基碳纳米管催化膜的制备及高效去除四环素

赵钰; 林海波; 毕秋艳; 王晓; 张国亮; 刘富

doi:10.14133/j.cnki.1008-9357.20230309001

钴铁双金属基碳纳米管催化膜的制备及高效去除四环素

doi: 10.14133/j.cnki.1008-9357.20230309001

赵钰^{1, 2,},
林海波^{2, 3, ,},
毕秋艳⁴,
王晓⁴,
张国亮¹,
刘富^{2, 3, ,}

1.
浙江工业大学膜分离与水科学技术研究院, 杭州 310014
2.
中国科学院宁波材料技术与工程研究所,浙江, 宁波 315201
3.
中国科学院大学, 北京 100049
4.
青海大学化工学院, 西宁 810016

基金项目: 中科院国际伙伴计划全球共性挑战专项（181GJHZ2022038GC）；浙江省重点研发计划(2021C03170)

详细信息

作者简介:
赵钰：赵　钰（1997—），男，河南济源人，硕士生，主要研究方向为催化膜的制备。E-mail：zhaoyu@nimte.ac.cn

通讯作者:
林海波，E-mail：linhaibo@nimte.ac.cn

刘　富，E-mail：fu.liu@nimte.ac.cn

中图分类号: O63
计量
- 文章访问数: 33
- HTML全文浏览量: 11
- PDF下载量: 14
- 被引次数: 0
出版历程
- 收稿日期: 2023-03-29
- 录用日期: 2023-05-06
- 网络出版日期: 2023-05-12

Preparation and Efficient Tetracycline Removal of Co-Fe Bimetallic Carbon Nanotubes Catalytic Membranes

ZHAO Yu^{1, 2
,},
LIN Haibo^{2, 3
, ,},
BI Qiuyan⁴,
WANG Xiao⁴,
ZHANG Guoliang¹,
LIU Fu^{2, 3
, ,}

1.
Institute of Membrane Separation and Water Science and Technology, Zhejiang University of Technology, Hangzhou 310014, China
2.
Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, Zhejiang, China
3.
University of Chinese Academy of Sciences, Beijing 100049, China
4.
School of Chemical Engineering, Qinghai University, Xining 810016, China

摘要

摘要: 采用煅烧钻铁双金属的普鲁士蓝类似物（CoFe PBA）的方法获得了包裹钴铁合金的碳纳米管催化剂（CoFe@Cs），然后使用真空抽滤制备复合催化膜。通过扫描电子显微镜（SEM）、X射线衍射图谱（XRD）、X射线光电子能谱（XPS）等对样品的形貌及组成进行表征；以四环素（TC ）为目标污染物对所制备催化剂及催化膜的催化机理及性能进行测试。结果表明，改变煅烧温度可以有效调控碳纳米管催化剂的形貌及组成。其中，在900 °C煅烧温度下制备的碳纳米管催化剂（CoFe@Cs-900）主要产生以硫酸根自由基及单线态氧为主的活性氧物质，并可对TC进行快速的降解去除。由其组装的碳纳米管催化膜在24 h错流过滤中对TC的降解去除率大于99%，水通量保持在172 L/(m²·h)，表现出优异的膜催化降解性能。
- 催化膜 /
- 自组装 /
- 高级氧化 /
- 四环素 /
- 过一硫酸盐
Abstract: Carbon nanotube catalysts encapsulating cobalt-iron (CoFe) alloy nanoparticles (CoFe@Cs) were synthesized by calcination of cobalt-iron bimetallic Prussian Blue analogs (CoFe PBA), and further assembled on polyethersulfone (PES) membrane support by vacuum filtration to prepare composite catalytic membranes for catalytic activation of peroxymonosulfate (PMS) and efficient degradation of tetracycline (TC). The morphology and structure of the samples were analyzed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), the composition was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. Based on the morphology, composition, and performance, carbon nanotube catalysts (CoFe@Cs-900) were selected from the prepared series of CoFe@Cs, and further the reactive oxygen species (ROS) in the catalytic process was analyzed by reactive oxygen quenching experiments and electron paramagnetic resonance (EPR). The stability of the carbon nanotube catalytic membrane under long-term operation was tested under optimized conditions. The results showed that the calcination temperature played an important role in regulating the morphology and composition of the catalysts. Among them, the carbon nanotube catalyst prepared by calcination at 900 °C can produce the reactive oxygen species, including sulfate radicals (·SO₄^-) and singlet oxygen (¹O₂), for the rapid removal of tetracycline. The carbon nanotube catalytic membrane achieved more than 99% removal of TC in continuous 24 h cross-flow filtration, and the water flux was maintained at 172 L/(m²·h). Overall, the catalytic membrane showed excellent degradation performances and potential application.
- catalytic membrane /
- self-assembly /
- advanced oxidation /
- tetracycline /
- peroxymonosulfate

HTML全文

图 1 样品的SEM图片

Figure 1. SEM images of samples

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图 2 CoFe PBA和CoFe@Cs的XRD图谱

Figure 2. XRD spectra of CoFe PBA and CoFe@Cs

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图 3 样品的XPS图谱

Figure 3. XPS spectra of samples

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图 4 CoFe@Cs的拉曼光谱分析

Figure 4. Raman spectra of CoFe@Cs

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图 5 不同催化剂对TC的（a）吸附能力和（b）降解能力

Figure 5. (a) Adsorption capacity and (b) degradation capacity of different catalysts for TC

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图 6 CoFe@Cs-900的（a）TEM图像以及（b，c）EDS mapping图像

Figure 6. (a) TEM image and (b, c) EDS images of CoFe@Cs-900

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图 7 （a）活性氧淬灭实验以及（b～d）电子顺磁共振测试

Figure 7. (a) Reactive oxygen species quenching experiment and (b—d) electron paramagnetic resonance test

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图 8 催化膜的（a）表面、（b）放大后的表面以及（c）断面的SEM图；（d）接触角随时间的变化

Figure 8. SEM images of (a) surface, (b) enlarged surface and (c) cross-sectional of the catalytic membrane; (d) Contact angle changing with time

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图 9 催化剂负载前后膜孔径（a）及通量（b）

Figure 9. Membrane pore size (a) and flux (b) before and after catalyst loading

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图 10 PMS浓度（a）和pH（b）对催化膜催化性能的影响

Figure 10. Effect PMS concentration (a) and pH value (b) on the catalytic performance of the catalytic membrane

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图 11 （a）催化膜连续错流过滤24 h时的去除率及通量；（b）运行后关于催化膜表面的SEM照片

Figure 11. (a) Removal rate and flux of the catalytic membrane during continuous cross-flow filtration for 24 h; (b) SEM image of catalytic membrane surface after operation

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